Features of High-Temperature Thermal
Oxidative Degradation of Organic-Inorganic Compositions
Based on Poly(methyl methacrylate)
B. B. Troitskii, L. V. Khokhlova, V. N. Denisova, M. A. Novikova,
A. E. Golubev, V. I. Faerman, and T. I. Lopatina
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhni Novgorod, Russia
Received January 28, 2008
Abstract—Thermal oxidative degradation of organic-inorganic compositions based on poly(methyl
methacrylate) and the methyl methacrylate–methyl acrylate copolymer with tetrabutoxytitanium was studied by
ISSN 1070-4272, Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 6, pp. 1106–1110. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © B.B. Troitskii, L.V. Khokhlova, V.N. Denisova, M.A. Novikova, A.E. Golubev, V.I. Faerman, T.I. Lopatina, 2009, published in
Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 6, pp. 1046–1048.
It has been shown earlier [1–8] that С
fullerenes are effective inhibitors of high-temperature
(≥300°C) thermal-oxidative degradation (TOD) of poly-
(methyl methacrylate) (PMMA) and its copolymers.
Temperature and concentration limits of the inhibition
of the disintegration of polymers by fullerenes were
determined. It was found that their small concentra-
) effectively decelerate TOD
of PMMA and ММА copolymers at temperatures up to
340°C. Organic antioxidants (branched phenols,
amines, sulfur- and phosphorus-containing compounds)
traditionally applied in practice of the polymer stabiliza-
tion lose antioxidative properties at temperatures
higher than 270°C . However a high cost of
fullerenes hampers their practical use.
It was found [9, 10] that organic-inorganic PMMA
compositions with hydrolysates of various alkoxy-
silanes: tetraethoxysilane, phenyltrimethoxysilane, amino-
propyltriethoxysilane are more thermally stable than
PMMA at a high-temperature TOD. The greatest
stabilizing effect was observed for aminopropyltri-
ethoxysilane, its additions shift the maximum of the
thermal-oxidative degradation rate to the high tempera-
ture by 60–65°C. Unlike PMMA compositions (MMA
copolymers) with fullerenes, which have clearly
pronounced induction periods at high-tempera-ture
TOD, the hydrolysates of alkoxysilanes reduce the
TOD rate of polymers without an induction period.
The aim of the present work was to study high-
temperature oxidative decomposition of organic-in-
organic compositions obtained on the basis of PMMA
and the copolymer of ММА and methacrylic acid
(MAA) with tetrabuthoxytitanium (TBOT).
Tetrabuthoxytitanium was purified by vacuum
Poly(methyl methacrylate) was obtained according
to the ordinary procedure  in sealed ampoules by
ММА batch polymerization in the presence of 0.4% of
dinitrile of azoisobutyric acid (AIBN) as the initiator.
Before polymerization ММА was purified by vacuum
distillation and deoxygenated by triple freezing a
reaction mixture in a vacuum by liquid nitrogen.
Ampoules were heated up at 70 (3 h), 90 (4 h), and
120°C (2.5 h). Samples of the ММА copolymer with
15 mol % of MAA were obtained in a similar way.
The ММА polymerization and ММА copoly-
merization with MAA were carried out with adding
various amounts (from 0.5 up to 20 wt %) of TBOT to
a reaction mixture. To remove monomer residuels, the